SUNSCREEN CONTAINING A Glycine Betaine DERIVATIVE

Abstract

The present invention relates to a photoprotective composition comprising, in a physiologically acceptable medium, at least one photoprotective compound and a surfactant comprising at least one ester derivative or amide derivative of glycine betaine. It also relates to the cosmetic use of this photoprotective composition for protecting the skin against certain effects of UVA radiation, and also to this photoprotective composition for use thereof in the protection of the skin against erythema caused by UVB radiation. Finally, it relates to the use of the abovementioned surfactant for increasing the sand resistance of a photoprotective composition.

Description

[0001] PHOTOPROTECTIVE COMPOSITION COMPRISING A DERIVATIVE OF

[0002] GLYCINE BETAINE

[0003] SUBJECT OF THE INVENTION

[0004] The present invention relates to a photoprotective composition comprising, in a physiologically acceptable medium, at least one photoprotective compound and a surfactant comprising at least one glycine betaine ester or amide derivative. It also relates to the cosmetic use of this photoprotective composition for protecting the skin against certain effects of UVA, as well as this photoprotective composition for its use in protecting the skin against erythema due to UVB. Finally, it relates to the use of the aforementioned surfactant for increasing the sand resistance of a photoprotective composition.

[0005] BACKGROUND OF THE INVENTION

[0006] In addition to causing burns, UV rays are known to be involved in the production of free radicals, which themselves lead to various changes in the skin, including skin aging, dryness, and the formation of pigment spots and uneven skin tone.

[0007] Photoprotective compositions used to protect the skin against the effects of UV rays are generally in the form of an emulsion, of the oil-in-water or water-in-oil type, which contains, at various concentrations, one or more lipophilic organic filters and / or mineral nanopigments of metal oxides, capable of selectively absorbing harmful UV radiation, these filters and their quantities being selected according to the desired sun protection factor. In such emulsions, the hydrophilic filters are present in the aqueous phase and the lipophilic filters (often the majority) are present in the fatty phase.

[0008] These emulsions generally contain a significant amount of oil necessary for the solubilization of lipophilic UV filters and therefore often have a greasy and sticky feel that may discourage consumers from using them. For this reason, oil-in-water emulsions are generally more appreciated by consumers, particularly due to their pleasant feel and their presentation in the form of non-greasy milk or cream. However, they also lose their effectiveness against UV rays more easily when they come into contact with water, when swimming in the sea or in a swimming pool, in the shower or when practicing water sports, since hydrophilic filters tend to dissolve in water. As a result, sunscreen compositions containing them, alone or in combination with lipophilic filters, no longer provide the initial protection sought.Furthermore, sunscreen compositions often have poor resistance to sand, which affects their effectiveness at the seaside since the user is discouraged from reapplying on sandy skin. Grains of sand stuck to the skin also cause irritation when rubbed.

[0009] It would therefore be useful to have photoprotective compositions with a non-greasy feel and good resistance to water and / or sand.

[0010] It has already been proposed to use cationic surfactants to reduce the greasy feel of oil-rich skin care compositions and to improve the water resistance, but also the sand resistance, of photoprotective compositions (HAPPI, December 2009, 62-65). However, a number of these compounds, in particular quaternary alkylammonium salts, such as distearyldimonium chloride and behentrimonium chloride, as well as amidoquats, such as palmitamidopropyltrimonium chloride, show insufficient biodegradability and ecotoxicity. There is therefore a need to develop photoprotective compositions that are more environmentally friendly.

[0011] Among the bio-based cationic agents, it has already been suggested to use an esterquat, distearoylethyldimonium chloride or DSEDC (Varisoft ®of EVONIK), in skin protection compositions, in particular in sunscreen compositions. However, this compound can only be formulated in an acidic medium and more precisely at a pH below 5 and generally below 4.5. However, the pH of healthy skin, which is determined by the composition of the hydrolipidic film present on its surface, is on average 5.5. It would therefore be desirable to have compounds capable of being formulated in a wider pH range and in particular up to a pH of 5.5. Furthermore, the aforementioned cationic surfactants are not easily compatible with anionic additives, some of which are commonly used as dispersants for UV filters, which further increases their formulation constraints.

[0012] The Applicant has now discovered, unexpectedly and surprisingly, that certain glycine betaine derivatives make it possible to improve the sand resistance of photoprotective compositions. It has also been observed that these compounds can be formulated at a pH of up to 5.5 and in oil-rich compositions, without adversely affecting the stability or sensory properties of these compositions.

[0013] These surfactants are also biodegradable and have very low ecotoxicity, which is even lower than that of DSEDC.

[0014] Patent applications WO 2005 / 121294 and WO 2015 / 078893 describe leave-on cosmetic compositions, in particular sunscreen compositions, containing glycine betaine ester or amide salts. In both cases, however, these glycine betaine derivatives are present in the form of surfactant compositions additionally containing optionally cationized alkylpolyglycosides.

[0015] To the Applicant's knowledge, however, it has never been suggested to use for the above-mentioned purposes long-chain glycine betaine ester or amide salts, as such or in the form of surfactant compositions free of possibly cationized alkylpolyglycosides.

[0016] SUMMARY OF THE INVENTION

[0017] The subject of the invention is a photoprotective composition comprising, in a physiologically acceptable medium, at least one photoprotective compound and a surfactant comprising at least one glycine betaine derivative of formula (1): X n [(CH3)3N + -CH2-COZ- R] n where Z denotes an oxygen atom or an -NH group, R is a linear or branched, saturated or unsaturated alkyl group comprising from 8 to 24 carbon atoms, X is an organic or inorganic anion, and n is 1 or 2, it being understood that said photoprotective composition does not contain any optionally cationized alkylpolyglycoside.

[0018] It also relates to the cosmetic use of the photoprotective composition mentioned above to protect the skin against the effects of UVA rays chosen from: the signs of skin aging, in particular wrinkles, sagging skin, loss of suppleness and / or elasticity of the skin; roughness of the skin; loss of radiance of the complexion; unevenness of the complexion and in particular pigment spots; and / or dryness of the skin. It also relates to a cosmetic process for protecting the skin against the effects of UVA rays chosen from: the signs of skin aging, in particular wrinkles, sagging skin, loss of suppleness and / or elasticity of the skin; roughness of the skin; loss of radiance of the complexion; unevenness of the complexion and in particular pigment spots; and / or dryness of the skin, comprising the topical application to the skin of the aforementioned photoprotective composition.

[0019] Another subject of this invention relates to a photoprotective composition as defined above, for its use in protecting the skin against erythema due to UVB.

[0020] Yet another subject of the present invention relates to the use of a surfactant as defined above for increasing the sand resistance of a photoprotective composition.

[0021] DETAILED DESCRIPTION

[0022] The present invention relates to a photoprotective composition containing at least one glycine betaine derivative of given formula. By "photoprotective composition" is meant a composition containing, in a physiologically acceptable medium, at least one photoprotective compound in a quantity sufficient to block or absorb UV rays, preferably at least one organic or inorganic UV-A and / or UV-B filter. It generally provides the skin with protection against UV rays, determined by its Sun Protection Factor, of at least 15, or even at least 30, for example a Sun Protection Factor of 15, 20, 30 or 50. It is a leave-on composition. By "leave-on" is meant that the composition is suitable and intended to be applied to the skin and left in place for at least one hour, before being removed by rinsing with water and / or using a cleansing composition.

[0023] This photoprotective composition contains a surfactant based on at least one glycine betaine derivative, which is an ester or amide salt of glycine betaine. These two types of glycine betaine derivatives, as well as their preparation processes, will now be described in more detail.

[0024] I. Glycine betaine ester salts Glycine betaine ester salts may be obtained by a process comprising the successive steps of: (1) reacting glycine betaine or one of its salts with at least one linear or branched, saturated or unsaturated fatty alcohol containing from 8 to 24 carbon atoms, in the presence of an organic or inorganic acid;

[0025] (2) cooling the reaction medium to a temperature of 20 to 90°C; and

[0026] (3) recover the surfactant composition thus obtained.

[0027] The first step in this process is to esterify glycine betaine, or trimethylglycine. Glycine betaine can be of plant or synthetic origin. It is necessary to protonate it beforehand using an organic or inorganic acid, since it is in zwitterionic form (presence of a carboxylate function). The acid can be chosen in particular from inorganic acids such as hydrochloric acid, sulfuric acid, perhalohydric acids, such as perchloric acid, and mixtures thereof.Alternatively, it may be chosen from organic acids, such as alkyl sulfuric acids, for example decyl or lauryl sulfuric acid; aryl sulfonic acids, such as benzene sulfonic acid, paratoluene sulfonic acid; alkyl sulfonic acids, such as triflic acid, methanesulfonic acid, ethanesulfonic acid, decylsulfonic acid, lauryl sulfonic acid or camphorsulfonic acid; sulfosuccinic acid; and mixtures thereof. Lewis acids may also be used. Preferably, it is an alkyl sulfonic acid and in particular methanesulfonic acid, since it is readily biodegradable.

[0028] During esterification, the acid function of the salified betaine is reacted with a fatty alcohol, resulting in a glycine betaine ester in salt form. By "fatty alcohol" is meant a linear or branched (preferably linear), saturated or unsaturated alcohol, comprising from 8 to 24 carbon atoms. Examples of such fatty alcohols may be selected from the group consisting of: octanol (C8:0), decanol (00:0), undecanol (01:0), lauryl alcohol (02:0), myristyl alcohol (04:0), cetyl alcohol (06:0), palmitoleyl alcohol (06:1), stearyl alcohol (08:0), oleyl alcohol (08:1), linoleyl alcohol (08:2), linolenic alcohol (08:3), arachidic alcohol (C20:0), arachidonic alcohol (C20:4), behenyl alcohol (C22:0), 2-hexyldecanol, 2-octyldodecanol, 2-decyltetradecanol and mixtures thereof.Mixtures of fatty alcohols which can be used may be produced from one or more vegetable oils and in particular from soybean, olive, sunflower, corn, palm, copra, cottonseed, linseed, wheat germ, safflower or rapeseed oil, for example. It is preferred according to the invention to use one or more alcohols containing from 16 to 22 carbon atoms and more preferably a mixture of such fatty alcohols.

[0029] The esterification reaction generally takes place in the absence of solvent. The water produced during the reaction also contributes to the solubilization of glycine betaine in the reaction mixture.

[0030] For carrying out this reaction, it is possible, for example, to use from 0.8 to 6.0 equivalents, preferably from 0.8 to 2 equivalents, for example from 0.9 to 1.0 equivalents, or alternatively from 1.1 to 1.8 equivalents, preferably in this case from 1.2 to 1.6 equivalents and, better still, from 1.3 to 1.5 equivalents of fatty alcohol or in a second alternative from 4.0 to 6.0 equivalents, preferably in this case from 4.5 to 5.5 equivalents and, better still, from 4.8 to 5.2 equivalents of fatty alcohol.

[0031] Advantageously, from 1.01 to 3.0 equivalents, preferably from 1.5 to 2.0 equivalents, for example from 1.5 to 1.9 equivalents, and preferably from 1.5 to 1.7 molar equivalents of organic or inorganic acid are further used, or alternatively from 1.02 to 1.08 equivalents, preferably in this case from 1.03 to 1.07 equivalents and, more preferably, from 1.04 to 1.06 molar equivalents of organic or inorganic acid per 1 equivalent of glycine betaine. The esterification is carried out at a temperature ranging, for example, from 120 to 180°C, preferably from 150 to 180°C. The reaction can be carried out under atmospheric pressure or preferably under reduced pressure, for example at a pressure of 10 to 600 mbar. The pressure will generally be lower the longer the chain length of the fatty alcohol involved. The reaction medium is then cooled to a temperature of 20 to 90°C.

[0032] The surfactant composition thus obtained is then recovered, which contains at least one glycine betaine ester salt of formula X n [(CH3)3N + -CH2-COOR] n where: X is an organic or inorganic anion, R is an alkyl radical corresponding to the fatty alcohol R-OH used in the esterification reaction, and n is 1 or 2.

[0033] The anion X is derived from the acid used in the first step of the process and may therefore in particular be a chloride, a sulfate, a perchlorate, an alkyl sulfate ion, in particular decyl sulfate or lauryl sulfate, an arylsulfonate ion, in particular benzene sulfonate, paratoluene sulfonate, an alkylsulfonate ion, in particular triflate, methanesulfonate, ethanesulfonate, decylsulfonate, laurylsulfonate, camphorsulfonate, or a sulfosuccinate ion. It is preferred according to the invention that X is chosen from alkylsulfonates and arylsulfonates, in particular from methanesulfonate, ethanesulfonate, triflate, paratoluenesulfonate and camphorsulfonate ions. It is advantageously the methanesulfonate ion.

[0034] The radical R can for its part be chosen from the groups octyl (C8:0), decyl (00:0), undecyl (01:0), lauryl (02:0), myristyl (04:0), cetyl (06:0), palmitoleyl (06:1), stearyl (08:0), oleyl (08:1), linoleyl (08:2), linolenyl (08:3), arachidyl (C20:0), arachidonyl (C20:4), behenyl (C22:0), 2-hexyldecyl, 2-octyldodecyl and 2-decyltetradecyl.

[0035] It is understood that, in the case where several fatty alcohols are used in the esterification reaction, the surfactant composition obtained will comprise several salts of glycine betaine esters. The expression "a salt of glycine betaine ester" must therefore be understood, in the context of this description and unless otherwise indicated, as referring to one or more of these salts.

[0036] The process described above makes it possible more precisely to obtain a surfactant composition containing the following constituents:

[0037] (a) at least one glycine betaine ester salt of formula (1): X n [(CH3)3N + -CH2-COO-R] n ,

[0038] (b) at least one fatty alcohol of formula R-OH,

[0039] (c) an organic or inorganic acid of formula XH,

[0040] (d) a glycine betaine salt of formula C h [(ϋ¾)3N + -O¾-000H], and

[0041] (e) optionally, at least one dialkyl ether of formula ROR, where R is a linear or branched, saturated or unsaturated alkyl group comprising from 8 to 24 carbon atoms, and preferably from 16 to 22 carbon atoms, X is an organic or inorganic anion and n is 1 or 2.

[0042] This surfactant composition may be used as such in the present invention. In this case, it generally contains from 15 to 85% by weight of glycine betaine ester salt.

[0043] It is understood that, within the scope of this description, the term "surfactant" means both a glycine betaine ester salt as described herein and the surfactant composition containing it, obtained as described above.

[0044] In a first variant, the surfactant composition contains: (a) from 65 to 85% by weight, preferably from 70 to 80% by weight, of glycine betaine ester salt,

[0045] (b) from 1 to 20% by weight, for example from 1 to 9% by weight or from 10 to 20% by weight, of fatty alcohol,

[0046] (c) from 1 to 20% by weight, for example from 5 to 15% by weight of organic or inorganic acid,

[0047] (d) from 1 to 20% by weight, for example from 2 to 15% by weight, of glycine betaine salt,

[0048] (e) from 0 to 15% by weight, for example from 2 to 10% by weight, of dialkyl ether.

[0049] In a second variant, the surfactant composition contains:

[0050] (a) from 15 to 45% by weight, preferably from 20 to 35%, more preferably from 25 to 30% by weight, of glycine betaine ester salt,

[0051] (b) from 50 to 70% by weight, for example from 60 to 70% by weight, of fatty alcohol,

[0052] (c) from 0 to 5% by weight, for example from 0 to 1% by weight of organic or inorganic acid,

[0053] (d) from 0 to 3% by weight, for example from 0 to 1% by weight, of glycine betaine salt,

[0054] (e) from 0 to 15% by weight, for example from 2 to 10% by weight, of dialkyl ether.

[0055] Advantageously, the surfactant composition does not contain any constituent other than components (a) to (e) above. Alternatively, the above process may include an additional step of isolating the glycine betaine ester salt present in this composition, which may be used as such in the present invention. In the latter case, the surfactant composition used according to the invention will comprise at least 90%, preferably at least 95%, or even at least 99% by weight of glycine betaine derivative.

[0056] II. Glycine betaine amide salts These glycine betaine derivatives can be prepared according to a process comprising the successive steps of:

[0057] (1) reacting glycine betaine or one of its salts with a linear or branched, saturated or unsaturated, C4-C8 alcohol, in the presence of an organic or inorganic acid, at a temperature ranging for example from 100 to 180°C and under reduced pressure;

[0058] (2) cooling the reaction medium to a temperature of 20 to 80°C;

[0059] (3) adding one or more alkylamines containing from 8 to 24 carbon atoms;

[0060] (4) remove residual alcohol; and

[0061] (5) recovering the surfactant composition thus obtained. The first step of this process consists of an esterification reaction of glycine betaine, which can be carried out in a similar manner to the production of glycine betaine esters, except that one or more linear and / or branched C4-C8 alcohol(s) are used in the presence of the acid which can be chosen from those described above. Examples of such alcohols include butanol, pentanol, 3-methylbutan-1-ol (or isoamyl alcohol), fusel alcohol (mixture of pentanol, 2-methylbutan-1-ol and 3-methylbutan-1-ol), hexanol, heptanol, octanol and mixtures thereof. By "butanol" is meant in this description "-butanol, isobutanol and sec-butanol. Butanol, and more particularly "-butanol, is preferred for use in this invention.This reaction is generally carried out in the absence of any solvent, the alcohol used constituting both the reactant and the medium. The water produced during the reaction also contributes to the solubilization of the glycine betaine in the reaction mixture. It is generally possible to use from 1.1 to 20 equivalents, for example from 2 to 4 equivalents, of linear or branched C4-C8 alcohol and from 1.0 to 1.5 equivalents of sulfonic acid, for example from 1.0 to 1.2 equivalents and preferably 1.1 equivalents of sulfonic acid, per 1 equivalent of glycine betaine. The esterification can be carried out at a temperature of 100 to 180°C, preferably from 100 to 160°C, more preferably from 120 to 150°C or from 130 to 160°C under atmospheric pressure or under reduced pressure.

[0062] The product of the esterification reaction may or may not be treated so as to separate the salt of the glycine betaine ester formed from the reaction medium. To do this, for example, the reaction medium may be filtered, which separates the aforementioned salified ester, soluble in alcohol, from the other constituents which are not soluble.

[0063] One or more C8-C24 alkylamine(s) are then added either to the reaction medium or to the isolated ester. Examples of such amines are: octylamine, decylamine, laurylamine, tetradecylamine, hexadecylamine, octadecylamine, docosanylamine, eicosanylamine and mixtures thereof. According to the invention, it is preferred to use one or more amines containing from 16 to 22 carbon atoms and more preferably a mixture of such amines.

[0064] In this step, the alkylamine is advantageously used in molten form. The amount of alkylamine(s) added may, for example, represent from 0.9 to 1.5 equivalents and preferably from 1.0 to 1.2 equivalents per 1 equivalent of glycine betaine initially used. This aminolysis reaction is typically carried out at a temperature of 50 to 180°C and preferably from 120 to 140°C, under reduced pressure, for example under a pressure of 1 to 30 mbar. In parallel with the aminolysis reaction, the alcohol is removed by distillation under reduced pressure. The aminolysis reaction and the distillation take place for a period of 1 to 7 hours, in particular 3 to 5 hours.

[0065] The surfactant composition thus obtained is then recovered.

[0066] This process makes it possible to obtain a surfactant composition comprising:

[0067] (a) one or more glycine betaine amide salt(s) of formula (1): C h [(ϋ¾)3N + -O¾-00NH-

[0068] R] n ;

[0069] (b) one or more alkylammonium salt(s) of formula (2): X n [NH3 + R] n ;

[0070] (c) one or more glycine betaine ester salt(s) of formula (3): C h [(0¾)3N + -CH2-COOR'] n where R' is a linear or branched, saturated or unsaturated alkyl radical containing from 4 to 8 carbon atoms; and

[0071] (d) glycine betaine of formula (4): (CH3)3N + -CH2-COO; where R is a linear or branched, saturated or unsaturated alkyl group comprising from 8 to 24 carbon atoms, preferably from 16 to 22 carbon atoms, X is an organic or inorganic anion and n is 1 or 2.

[0072] It is understood that, within the scope of this description, the term "surfactant" means both a glycine betaine amide salt as described herein and the surfactant composition containing it, obtained as described above.

[0073] This surfactant composition may be used as such in the present invention. In this case, it generally contains from 60 to 98% by weight, for example from 70 to 80% by weight, of glycine betaine amide salt. Component (b) may represent from 0 to 25% by weight, for example from 15 to 20% by weight, component (c) from 0 to 15% by weight, for example from 5 to 10% by weight, and component (d) from 0 to 5% by weight, relative to the total weight of the surfactant composition. Advantageously, the latter does not contain any other component than components (a) to (d) above. Alternatively, the above process may include an additional step of isolating the glycine betaine amide salt present in this composition, which may be used as such in the present invention. In the latter case, the surfactant composition will comprise at least 90%, preferably at least 95%, or even at least 99% by weight of glycine betaine derivative.In all cases, it is preferred that the surfactant composition containing a glycine betaine ester or amide salt as defined above, and / or the photoprotective composition comprising it, does not contain any optionally cationized alkylpolyglycoside.

[0074] For use in the present invention, preferred are glycine betaine ester salts and in particular salts of esters containing from 14 to 22 carbon atoms, preferably from 16 to 22 carbon atoms and more preferably from 18 to 22 carbon atoms.

[0075] For the implementation of the present invention, a photoprotective composition is used containing a surfactant as described above, preferably in an amount of 1 to 15% by weight, more preferably 2 to 8% by weight, relative to the weight of the photoprotective composition, when it is a surfactant composition as described above. The photoprotective composition generally contains 0.5 to 8% by weight, and preferably 1 to 5% by weight, of glycine betaine derivative according to the invention.

[0076] The photoprotective composition contains a physiologically acceptable medium, i.e. compatible with the skin, in particular cosmetically acceptable, i.e. which does not generate tingling or redness incompatible with cosmetic use. This medium preferably contains an aqueous phase containing water and / or glycerin and a fatty phase to form an emulsion. This emulsion may be of the oil-in-water (O / W), oil-in-glycerin, water-in-oil (W / O), water-in-glycerin or multiple (for example W / O / W) type. This emulsion is preferably of the oil-in-water type.

[0077] The aqueous phase may further contain at least one aqueous gelling agent. The term "aqueous gelling agent" means a polymeric compound capable of immobilizing water molecules by hydrating and thus increasing the viscosity of the aqueous phase. Such a gelling agent may be chosen from: polysaccharides, such as: cellulose and its derivatives, modified starches, carrageenan, agar agar, xanthan gum and vegetable gums such as guar, tara or carob gum; synthetic polymers and in particular homopolymers of sodium acrylate which are optionally crosslinked, as well as acrylic copolymers, in particular copolymers of sodium acrylate and / or alkyl (meth)acrylate and / or hydroxyalkyl (meth)acrylate and / or (polyethoxy)alkyl (meth)acrylate, with optionally at least one other monomer, advantageously 2-acrylamido-2-methylpropane sulfonic acid (AMPS), these copolymers being optionally crosslinked; and mixtures thereof.

[0078] For its part, the fatty phase may comprise one or more volatile and / or non-volatile oils. Examples of volatile oils are branched alkanes, such as isododecane, and linear C10-C13 alkanes. Non-volatile oils include:

[0079] - esters of acids and mono-alcohols chosen from: mono- and polyesters of linear saturated C2-C10 (preferably C6-C10) acids and linear saturated C10-C8 (preferably C10-C14) mono-alcohols, mono- and polyesters of linear saturated C10-C20 acids and branched or unsaturated C3-C20 (preferably C3-C10) mono-alcohols; mono- and polyesters of branched or unsaturated C5-C20 acids and branched or unsaturated C5-C20 mono-alcohols; mono- and polyesters of branched or unsaturated C5-C20 acids and linear C2-C4 mono-alcohols;

[0080] - C6-C12 fatty acid triglycerides, such as caprylic and capric acid triglycerides and triheptanoin;

[0081] - branched and / or unsaturated C10-C20 fatty acids (such as linoleic acid);

[0082] - branched and / or unsaturated C10-C20 fatty alcohols (such as octyldodecanol and oleyl alcohol);

[0083] - hydrocarbons such as squalane (C30), in particular plant squalane extracted from olive oil, and hemisqualane (Cl 5);

[0084] - dialkyl carbonates, such as dicaprylyl carbonate and diethylhexyl carbonate;

[0085] - dialkyl ethers such as dicaprylyl ether; and

[0086] - their mixtures.

[0087] We can also cite vegetable oils which contain one or more of the aforementioned constituents.

[0088] Examples of esters of acids and monoalcohols include monoesters such as the mixture of coco caprate and caprylate, ethyl macadamiate, shea butter ethyl ester, isostearyl isostearate, isononyl isononanoate, ethylhexyl isononanoate, hexyl neopentanoate, ethylhexyl neopentanoate, isostearyl neopentanoate, isodecyl neopentanoate, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, ethylhexyl palmitate, hexyl laurate, isoamyl laurate, cetostearyl nonanoate, propylheptyl capylate and mixtures thereof. Other useful esters are diesters of acids and monoalcohols such as disopropyl adipate, diethylhexyl adipate, diisopropyl sebacate and diisoamyl sebacate.

[0089] Examples of vegetable oils include wheat germ, sunflower, linseed, argan, hibiscus, coriander, grape seed, corn, apricot, castor, shea, avocado, olive, soybean, sweet almond, palm, rapeseed, cottonseed, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, blackcurrant, evening primrose, lavender, borage, millet, barley, quinoa, rye, safflower, candlenut, passionflower, musk rose, Echium, camelina or camellia.

[0090] The fatty phase may further comprise at least one fatty phase structuring agent. By "fatty phase structuring agent" is meant a compound capable of thickening the oils contained in the composition, chosen in particular from waxes, fatty phase gelling agents and pasty fatty substances, as well as mixtures thereof.

[0091] In one embodiment of the invention, the photoprotective composition contains at least 20% by weight, preferably at least 30% by weight, more preferably at least 40% by weight or even at least 50% by weight of oil(s). In certain embodiments, the photoprotective composition may even comprise at least 60%, for example at least 70%, or even at least 80% by weight of oil(s). It has in fact been observed that the glycine betaine derivatives according to the invention make it possible to give a non-greasy or even powdery feel to these compositions, even when they contain a high level of oil(s).

[0092] The photoprotective composition contains at least one organic or inorganic UV filter, or a mixture thereof, preferably at least one insoluble UV filter. By UV filter is meant any system capable of filtering UVA and / or UV-B radiation. By insoluble UV filter is meant, for the purposes of the present invention, UV filters insoluble in cosmetic media generally used in sunscreen formulations and more particularly whose solubility in water at 25°C is less than 0.1% by weight and whose solubility in paraffin oil at 25°C is less than 1% by weight.

[0093] UV filters can be UV-B filters (absorption in the range 290 to 320 nm), UV-A filters (absorption in the range 320 to 380 nm) or broad-spectrum filters (absorption in the range 290 to 380 nm). Generally, it is preferred to use a combination of at least two UV filters, preferably at least one UV-A filter and at least one UV-B filter. Examples of organic UV filters include the following, designated by their INCI name:

[0094] • Butyl methoxydibenzoylmethane or Avobenzone

[0095] • Para-aminobenzoic acid (PABA) and its derivatives such as Ethyl PABA, Ethyl dihydroxypropyl PABA, Ethylhexyl dimethyl PABA, Glyceryl PABA, PEG-25 PABA

[0096] • Salicylic acid derivatives including: Homosalate, Ethylhexyl salicylate, Dipropylene glycol salicylate, TEA salicylate

[0097] • b,b-Diphenylacrylate derivatives, such as Octocrylene, Etocrylene

[0098] • Les dérivés de benzophénone, dont Benzophenone- 1 , Benzophenone-2, Benzophenone-

[0099] 3, Benzophenone-4, Benzophenone-5, Benzophenone- 6, Benzophenone- 8,

[0100] Benzophenone-9, Benzophenone- 12

[0101] • Diethylaminohydroxybenzoylhexyl benzoate (“Uvinul A Plus” de BASF)

[0102] • Les dérivés de benzylidènecamphre, tels que 3-Benzylidenecamphor, 4- Methylbenzylidenecamphor (“Eusolex 6300” de Merck), Benzylidenecamphorsulfonic acid, Camphor benzalkonium methosulfate, Terephthalylidenedicamphorsulfonic acid, Polyacrylamidomethylbenzylidenecamphor

[0103] • Les dérivés de phénylbenzimidazole, dont Phenylbenzimidazolesulfonic acid (“Eusolex 232” de Merck), Disodium phenyl dibenzimidazole tetrasulfonate

[0104] • Les dérivés de phénylbenzotriazole, dont Drometrizole trisiloxane,

[0105] Methylenebis(benzotriazolyl)tetramethylbutylphenol (“Tinosorb M” de Ciba)

[0106] • Triazine derivatives, such as Bis(ethylhexyloxyphenol)methoxyphenyl triazine (“Tinosorb S” from Ciba), Ethylhexyltriazone (“Uvinul T150” from BASF), Diethylhexylbutamidotriazone (“Uvasorb HEB” from Sigma 3V), 2,4,6-tris(diisobutyl 4'-aminobenzalmalonate)-s-triazine

[0107] • Anthranilic derivatives, including Menthyl anthranilate

[0108] • Imidazoline derivatives, such as Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate

[0109] • Benzylmalonate derivatives such as polyorganosiloxanes containing benzylmalonate functions, notably Polysilicone-15 (“Parsol SLX” from Hoffmann LaRoche)

[0110] • 4,4-Diarylbutadiene derivatives, including 1,1-Dicarboxy(2,2'-dimethylpropyl)-4,4-diphenyl-butadiene • Benzoxazole derivatives, such as 2,4-bis[5-(1-dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine ("Uvasorb K2A" from Sigma 3V)

[0111] • merocyanine derivatives such as those described in WO 2004006878,

[0112] • and their mixtures.

[0113] The UV filters are generally used in the photoprotective composition according to the invention in an amount of 0.05% to 30% by weight, preferably 5% to 25% by weight, more preferably 10% to 20% by weight, relative to the total weight of the photoprotective composition.

[0114] According to a preferred embodiment, this photoprotective composition also contains at least one anti-aging active ingredient, in particular an active ingredient suitable for preventing and / or treating wrinkles, sagging skin and / or the formation of pigment spots, which may in particular be chosen from anti-radical or anti-oxidant agents, agents stimulating the differentiation and / or proliferation of keratinocytes and / or fibroblasts; agents stimulating the synthesis of glycosaminoglycans and / or collagen and / or dermo-epidermal anchoring fibrils and / or elastic fibers; agents preventing the degradation of collagen and / or glycosaminoglycans and / or dermo-epidermal anchoring fibrils and / or elastic fibers; anti-glycation agents; depigmenting agents and / or agents inhibiting melanogenesis; and mixtures thereof.

[0115] Examples of such anti-aging actives include: ascorbic acid, its salts, ethers and esters, including ascorbyl glucoside; adenosine; plant proteins and their hydrolysates; polypeptides and pseudodipeptides; silanes such as methylsilanol mannuronate; alpha- and beta-hydroxy acids; and mixtures thereof.

[0116] According to an advantageous embodiment of the invention, the photoprotective composition comprises at least one antioxidant active ingredient, which makes it possible to limit the oxidative damage caused by UV rays, in particular vitamins such as ascorbic acid and its derivatives and tocopherol and its derivatives, ubiquinone or coenzyme Q10, polyphenols such as resveratrol and its derivatives, as well as plant extracts containing them, in particular pomegranate, grape or green tea extracts; carotenoids such as lycopene as well as plant extracts containing them; and mixtures thereof. The photoprotective composition according to the invention may also contain at least one self-tanning agent, such as DHA and / or erythrulose.

[0117] Alternatively or additionally, the photoprotective composition according to the invention may comprise at least one moisturizing or humectant agent, chosen for example from polyols such as propylene glycol, glycerin, pentylene glycol, xylitol or sorbitol; urea; hyaluronic acid and its salts; amino acids; and mixtures thereof.

[0118] The photoprotective composition according to the invention may further contain different constituents which may be dispersed in the fatty phase and / or in the aqueous phase which it contains, provided that these are compatible with topical application to the skin.

[0119] It may thus contain at least one oil-in-water or water-in-oil emulsifier, generally non-ionic, such as polyoxyethylene esters, optionally polyethoxylated sorbitan esters, optionally polyethoxylated fatty acid and glycerol esters, sucrose esters, fatty alcohol and sugar ethers such as alkyl glucosides, and mixtures thereof. The emulsifiers may represent from 2 to 10% and preferably from 4 to 6% of the total weight of the composition.

[0120] In one embodiment of the invention, the photoprotective composition does not contain any emulsifier other than the surfactant composition described above. In particular, in the case of glycine betaine esters, the surfactant composition containing them also naturally contains a more or less significant quantity of fatty alcohol which gives it remarkable emulsifying properties.

[0121] The photoprotective composition according to the invention may also comprise additives chosen in particular from: powdery fillers; perfumes; sequestering agents; pH adjusters; preservatives; pigments; dyes; and mixtures thereof.

[0122] Examples of pH adjusters are acetic acid / sodium acetate and succinic acid / sodium succinate buffer solutions, sodium gluconate and sodium lactate. The pH of the photoprotective composition may be in particular between 2 and 6, preferably between 4 and 5.5 and, better still, between 5 and 5.5. The photoprotective composition may have a liquid or semi-liquid consistency or a solid consistency. It may be in any form suitable for topical application to the skin and in particular in the form of milk, cream, lotion or gel.

[0123] It may in particular be packaged in a tube, a pump bottle or a jar. Alternatively, it may be packaged in an aerosol container, in order to ensure application of the composition in vaporized form. In the latter case, the photoprotective composition preferably comprises at least one propellant.

[0124] Use

[0125] The photoprotective composition according to the invention is suitable and intended to be applied to the skin. By "skin" is meant the entire skin of the body excluding the scalp and in particular the face, neck, décolleté, hands, arms, legs and / or stomach.

[0126] It can be applied to the skin once or several times a day, in order to protect it against the effects of UV rays, in particular against erythema due to UVB rays and / or to prevent and / or slow down the deterioration of the appearance of the skin caused by its exposure to UVA rays, in particular to prevent and / or slow down the signs of skin aging, in particular wrinkles, sagging skin, loss of suppleness and / or elasticity of the skin; roughness of the skin; loss of radiance of the complexion; unevenness of the complexion and in particular pigment spots; and / or dryness of the skin.

[0127] The surfactant according to the invention makes it possible to increase the sand resistance of the photoprotective composition.

[0128] The sand resistance capacity of the photoprotective compositions according to the invention can be evaluated by applying 0.3 g of composition to the forearm of a panelist and then, after one minute, by spraying fine sand (30 mL) onto the treated surface. Alternatively, the modified application protocol described in the examples below can be used. The panelist then claps his hands three times to remove the sand. The sand remaining on the forearm is then recovered by rinsing, dried and weighed. The surfactant according to the invention can also increase the water resistance of the photoprotective composition. Indeed, the cationic charge of this surfactant has a certain affinity for the keratin of the skin (overall negatively charged), thus making it possible to form a hydrophobic film on the skin (thanks to the lipophilic chains of the surfactant) which creates a water barrier.

[0129] The water resistance of the photoprotective compositions according to the invention can be measured using two methods. In the first method, the water resistance is evaluated in vitro by measuring the contact angle of a drop of water on a surface coated with the photoprotective composition. The second method consists of implementing the in vivo test recommended by COLIPA in "Guidelines for Evaluating Sun Product Water Resistance (December 2005)", i.e. measuring the ratio of the SPL after the action of water compared to the SPL before the action of water. The SPL reflects the increase in the duration of solar irradiation permitted using the composition. It corresponds to the quotient of the duration to reach the erythema threshold (minimal erythema dose or "MED") in the presence of the photoprotective composition (protected skin) compared to the duration measured in the absence of this composition (unprotected skin).SPL is determined in vivo on human skin according to COLIPA instructions. MED is the lowest dose of UV irradiation which, after 16-24 hours, generates a slight but clear reddening of the skin (sunburn, erythema). The irradiation sources are generally xenon lamps.

[0130] Regardless of the surfactant used (based on glycine betaine ester or amide), the surfactant composition used according to the invention can also protect the skin against the cutaneous effects of external aggressions. By "external aggressions" is meant in particular skin cleansing compositions, more particularly those containing at least one anionic surfactant, and / or environmental factors such as atmospheric pollutants and / or electromagnetic radiation with a wavelength between 280 and 500 nm, namely UV and blue light.

[0131] Pollutants, but also UV and blue light, are particularly likely to cause excessive production of free radials responsible for skin aging. The main atmospheric pollutants that can have a harmful effect on the skin are toxic gases (such as ozone, carbon monoxide, nitrogen or sulfur oxides), heavy metals, particularly those found in cigarette smoke (such as mercury, cadmium or lead), polycyclic aromatic hydrocarbons (or "PAHs", such as benzopyrene) and fine particles such as PM2.5, which are combustion residues on which a large quantity of organic and mineral compounds are adsorbed. For their part, anionic surfactants, and in particular sulfates used in hygiene and cleaning products, also tend to dry out the skin.Finally, the various chemical and physical aggressions to which the skin is subjected constantly modify the speed and quality of epidermal renewal. An alteration of the barrier function is thus observed, which manifests itself through various visible signs such as dry skin, the formation of superficial or deeper wrinkles, a dull complexion and / or the appearance of pigment spots.

[0132] The surfactant described above can thus prevent and / or slow down the deterioration of the appearance of the skin caused by external aggressions. It can therefore also be used in leave-on cosmetic compositions, in particular cosmetic skin care or makeup compositions (such as foundation).

[0133] The invention will be better understood in light of the following examples, which are given purely for illustrative purposes and are not intended to limit the scope of the invention, defined by the appended claims.

[0134] EXAMPLES

[0135] Example 1: Sand resistance test

[0136] The effect of a surfactant composition according to the invention on the sand resistance of a photoprotective composition was evaluated.

[0137] 1- Preparation of the surfactant composition

[0138] Glycine betaine (1.0 eq) and a mixture of fatty alcohols from C18 to C22 (5.0 eq) are introduced into a reactor. The set temperature at the mixture is set at 150 °C and the pressure is reduced to a value of 60 mbar. Once the pressure and temperature set points are reached, a 70% methanesulfonic acid solution (1.05 eq) is added to the reaction mixture. As soon as the addition is complete, the set temperature is brought back to 150 °C and the pressure is maintained at a value of 30 mbar. Six hours after the start of the introduction of the acid, the reaction mixture is allowed to cool to 80 °C, then the product is recovered, cooled to room temperature, and constitutes the surfactant composition according to the invention, which contains the following constituents: 2- Preparation of photoprotective compositions

[0139] Two photoprotective compositions were prepared in the form of an O / W emulsion containing the following constituents:

[0140] (1) Surfactant composition according to the invention, prepared as described above.

[0141] (2) Parsol Max ® from DSM 3- Sand resistance test

[0142] The sand resistance of Compositions A and B above was evaluated.

[0143] To do this, 10g of sand was sprinkled on a flat surface. At the same time, a 7x4 cm rectangle was drawn on the forearm of volunteers, into which 56g of composition A or B was then applied (at a rate of 2 mg / cm 2). The cream was rubbed in with a light massage, then the arm was left exposed to the air for 2 minutes. The forearm was then applied to the sand for 10 seconds. After 1 minute of application, the volunteers were asked to clap their hands three times with the same force. The amount of sand remaining stuck to the forearm was then calculated.

[0144] Three tests were carried out. The average of these tests was calculated and is reported in the table below:

[0145] These tests show that the surfactant composition according to the invention gives the photoprotective composition a resistance to sand significantly greater than that of other cationic surfactants. Example 2: Sunscreen compositions

[0146] Several types of sunscreen products can be prepared using surfactant compositions according to the invention, hereinafter identified by GBE or GBA, based respectively on glycine betaine ester or amide salts.

[0147] Sunscreen: Solid sunscreen SPF25: Cosmos SPF30 Sunscreen:

Claims

Demands 1. Photoprotective composition comprising, in a physiologically acceptable medium, at least one photoprotective compound and a surfactant comprising at least one glycine betaine derivative of formula (1): X n [(CH3)3N + -CH2-COZ-R] n where Z denotes an oxygen atom or an -NH group, R is a linear or branched alkyl group, saturated or unsaturated, comprising 8 to 24 carbon atoms, X is an organic or inorganic anion, and n is 1 or 2, it being understood that said photoprotective composition does not contain any alkylpolyglycoside possibly cationized.

2. Photoprotective composition according to claim 1, characterized in that the radical R is selected from the following groups: octyl (C8:0), decyl (00:0), undecyl (Cl 1:0), lauryl (02:0), myristyle (04:0), cetyl (06:0), palmitoleyl (06:1), stearyl (08:0), oleyl (08:1), linoleyl (08:2), linolenyl (08:3), arachidyl (C20:0), arachidyl (C20:4), behenyl (C22:0), 2-hexyldecyl, 2-octyldodecyl and 2-decyltetradecyl.

3. Photoprotective composition according to claim 1 or 2, characterized in that the anion X is selected from a chloride, a sulfate, a perchlorate, an alkylsulfate ion, in particular decylsulfate or laurylsulfate, an arylsulfonate ion, in particular benzene sulfonate, paratoluene sulfonate, an alkylsulfonate ion, in particular triflate, methanesulfonate, ethanesulfonate, decylsulfonate, laurylsulfonate, camphosulfonate, or a sulfosuccinate ion, preferably from the alkylsulfonates and the arylsulfonates, more particularly from the methanesulfonate, ethanesulfonate, triflate, paratoluenesulfonate and camphosulfonate ions, better, X is the methanesulfonate ion.

4. Photoprotective composition according to any one of claims 1 to 3, characterized in that the surfactant contains and is preferably composed of the following constituents: (a) at least one glycine betaine ester salt of formula (1): X n [(CH3)3N + -CH2-COO-R] n, (b) at least one fatty alcohol of formula R-OH, (c) an organic or inorganic acid of formula XH, and (d) a glycine betaine salt of formula X n [(CH3)3N + -CH2-COOH] n , where R is a linear or branched alkyl group, saturated or unsaturated, comprising from 8 to 24 carbon atoms, and preferably from 16 to 22 carbon atoms, X is an organic or inorganic anion and n is 1 or 2.

5. Photoprotective composition according to any one of claims 1 to 3, characterized in that the surfactant contains and is preferably composed of the following constituents: (a) one or more glycine betaine amide salt(s) of formula (1): C h [(ϋ¾)3N + -O¾-00NH- R] n ; (b) one or more alkylammonium salt(s) of formula (2): X n [NH3 + R] n ; (c) one or more glycine betaine ester salt(s) of formula (3): C h [(0¾)3N + -CH2-COOR'] n where R' is a linear or branched alkyl radical, saturated or unsaturated, containing 4 to 8 carbon atoms; and (d) of glycine betaine of formula (4): (CH3)3N + -CH2-COO ; where R is a linear or branched alkyl group, saturated or unsaturated, comprising 8 to 24 carbon atoms, preferably 16 to 22 carbon atoms, X is an organic or inorganic anion and n is 1 or 2.

6. Photoprotective composition as defined in any one of claims 1 to 5, for use in protecting the skin against erythema due to UVB.

7. Cosmetic use of the photoprotective composition according to any one of claims 1 to 5 to protect the skin against the effects of UVA selected from: signs of skin aging, including wrinkles, sagging skin, loss of suppleness and / or elasticity of the skin; roughness of the skin; loss of radiance of the complexion; unevenness of the complexion and in particular pigment spots; and / or dryness of the skin.

8. Cosmetic use according to claim 7, characterized in that the photoprotective composition is applied to the face, neck, décolletage, hands, arms, legs and / or stomach.

9. Cosmetic process for protecting the skin against the effects of UVA selected from: signs of skin aging, including wrinkles, sagging skin, loss of suppleness and / or elasticity of the skin; roughness of the skin; loss of radiance of the complexion; unevenness of the complexion and in particular pigment spots; and / or dryness of the skin, comprising topical application to the skin of the photoprotective composition according to any one of claims 1 to 5.

10. Use of a surfactant as defined in any one of claims 1 to 5 to increase the sand resistance of a photoprotective composition.